CN101945605B - Antimicrobial cellulose sponge and method of making - Google Patents

Antimicrobial cellulose sponge and method of making Download PDF

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CN101945605B
CN101945605B CN200880126660.7A CN200880126660A CN101945605B CN 101945605 B CN101945605 B CN 101945605B CN 200880126660 A CN200880126660 A CN 200880126660A CN 101945605 B CN101945605 B CN 101945605B
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cellulose sponge
biguanides
sponge
aliphatic
packing
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CN101945605A (en
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麦翰·T·张
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3M Innovative Properties Co
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44Guanidine; Derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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  • Detergent Compositions (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Washing And Drying Of Tableware (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Biguanide bonded within a cellulose sponge inhibits or prevents the growth of microorganisms such as bacteria, mold, and fungus within the cellulose sponge over the useful life of the cellulose sponge.

Description

Antimicrobial fibre element sponge and preparation method
Technical field
The present invention relates to cellulose sponge and a kind of method of preparing cellulose sponge, described cellulose sponge is permanent antimicrobial in its whole length of life.
Background technology
Cellulose sponge can be for clean kinds of surface.They generally under moistening a little condition packing and selling to consumer to keep its softness, and comprise antimicrobial to suppress growth of microorganism within the storage life.Yet due to long-term moistening environment, cellulose sponge is highly susceptible to grow bacterium and mould during use.The antimicrobial existing between the storage life is often rinsed, or becomes and lost efficacy or deficiency in cellulose sponge length of life.Therefore, because cellulose sponge is generally used in kitchen and bathroom, so the microbes of growing in sponge causes health problem in the family.Be starved of a kind of cellulose sponge, it has higher antimicrobial growth characteristics during use.
Summary of the invention
Although the antimicrobial that is often used in preserving cellulose sponge in its packing can not continue to work between the follow-up operating period, but have now found that, a kind of specific antimicrobial that is known as biguanides provides significant, lasting effect while using under enough concentration.Although by cyclic washing, biguanides still keeps being combined in cellulose sponge.When keeping existing and effectively time, the growth of microorganism in cellulose sponge will significantly reduce in the whole length of life of sponge by the biguanides of dry sponge weighing scale at least 0.02 % by weight.
For example, even at water, carry out rinsing and wringing out for 100 times after circulation the minimizing of processing to keep the cellulose sponge of at least 0.02 % by weight biguanides still to show 3 logarithm levels of growth of microorganism by biguanides.This is an important breakthrough, although and biguanides be called as the antimicrobial for conventional purposes, the unique application of the substantially permanent antimicrobial fibre element of this generation of biguanides sponge has potential important publilc health effect.
According to conjecture, different from many other antimicrobials, the Cationic functional groups of biguanides is combined with the anionic functional group of cellulose sponge material, thereby not only biguanides is kept in position, and allows biguanides keep active and can within short-term, reduce microorganism.
Therefore, the invention provides a kind of cellulose sponge, in this cellulose sponge, maintain antimicrobial, described antimicrobial suppresses or stops microorganism (for example, bacterium, mould and fungi) to grow in cellulose sponge in the whole length of life of cellulose sponge.In one embodiment, the cellulose sponge that has an antimicrobial is packaged in the airtight container that may comprise moisture.In this packing, maybe advantageously also in antimicrobial cleansing goods, comprise wetting agent, to reduce the water activity in packing and to suppress microbial growth in packing.
In one embodiment, described cellulose sponge comprises biguanides.After water carries out rinsing for 100 times and wrings out circulation, the biguanides of dry weight basis at least 0.02 % by weight of cellulose sponge is pressed in cellulose sponge maintenance, to obtain the minimizing of at least 3 logarithm levels of microorganism in cellulose sponge.
In another embodiment, press the dry weight basis of cellulose sponge, the biguanides that the cellulose sponge in packing comprises at least 0.4 % by weight.After taking-up water from packing carry out rinsing for 100 times and wring out circulation, press the dry weight basis of cellulose sponge, the biguanides of at least 0.02 % by weight is retained in sponge, to obtain the minimizing of at least 3 logarithm levels of microorganism in cellulose sponge.
In another embodiment, cellulose sponge is prepared by the following method, and described method comprises: cellulose sponge is provided; The input solution that comprises 0.1 to 2.0 % by weight biguanides is absorbed in cellulose sponge; And during cellulose sponge is packaged in and is packed.Press the dry weight basis of cellulose sponge, the biguanides that the cellulose sponge of packing comprises at least 0.4 % by weight.
In another embodiment, the cellulose sponge in packing comprises by the biguanides of the dry weight basis of cellulose sponge at least 1.25 % by weight and makes to pack interior water activity (a w) be less than 0.91 wetting agent.After cellulose sponge being taken out from packing and water carries out rinsing for 100 times and wring out circulation, press the dry weight basis of cellulose sponge, the biguanides of at least 0.5 % by weight is retained in cellulose sponge, to obtain 100% minimizing of microorganism in sponge.
In another embodiment, the method for preparing antimicrobial cleansing goods comprises: cellulose sponge is provided; The input solution that comprises at least 0.1 % by weight biguanides is absorbed in cellulose sponge; Biguanides is combined in cellulose sponge; During cellulose sponge is packaged in and is packed, wherein press the dry weight basis of cellulose sponge, the biguanides that the cellulose sponge of packing comprises at least 0.4 % by weight.
In another embodiment, the keep clean method of structure anti-microbe ability comprises: the cellulose sponge that comprises anionic functional group is provided; Input solution is absorbed in cellulose sponge, and described input solution comprises the biguanides with Cationic functional groups; The Cationic functional groups of biguanides and the anionic functional group of cellulose sponge are combined; Make cellulose sponge repeatedly be exposed to water to rinse.In conjunction with biguanides can form the minimizing of at least 3 logarithm levels of micro organism quantity in cellulose sponge.
It is also understood that according to the disclosure, other antimicrobials with Cationic functional groups will be also available, as long as described Cationic functional groups provides enough combination to realize the permanently effective resistance to growth of microorganism in cellulose sponge material.
The specific embodiment
For the cleaning article available in a period of time, in cleaning course, cleaning article itself should not become the source of accommodating and propagating microorganism.As long as be suitable for the environment of growth of microorganism, exist, cleaning article will be deteriorated.These microorganisms of bacterium and fungi normally make the deteriorated reason of product, while particularly occurring in packing before deteriorated use.Bacterium needs carbon source, applicable atmospheric environment, applicable environment temperature and pH and moisture to grow.Fungi has similar growth requirement, and different is that all fungies all need oxygen, and required moisture changes in a wider context compared with bacterium.Here growth is defined as the increase of total bacterial community, rather than the increase of individual bacterial cells.
Sponge is common cleaning article.Sponge is the lightweight with absorbent properties, the structure that fiber connects.They can be made by multiple different material, and these materials comprise that it is called as cellulose sponge herein such as the synthetic polymer of carbamate and natural polymer cellulose.Due to its outstanding water absorbing properties, cellulose sponge is a kind of cleaning article of uniqueness.Cellulose sponge is high-hydrophilic, has 10 times to the water-holding capacity of its deadweight.Cellulose sponge also demonstrates outstanding wet strength, and can confess fluid simultaneously and absorb liquid.
Generally speaking, cellulose sponge is by being dispersed in sodium sulfate crystal in prezenta and preparing.Once mix with prezenta, sodium sulfate crystal is with regard to the stripping cellulose sponge by heating prezenta, and prezenta is regenerated or be condensed into not dissolved state.This produces hole in cellulose sponge, thereby facilitates its high-hydroscopicity.Once regeneration, sponge is just rinsed prezenta.Should be appreciated that cellulose sponge can make by comprising raw-material multiple cellulose, for example (but being not limited to) timber, wood pulp, recycle cellulose sponge or other natural fibers.Should be appreciated that cellulose sponge can comprise additional material, for example dyestuff, spices, aromatic, surfactant and fortifying fibre.Fortifying fibre can be natural fiber, organize dust, loose shredded paper pulp fibres, cotton fiber.Natural fiber comprises cotton, wool, silk, hemp, bamboo, such as the viscose rayon of artificial silk.
The outstanding water absorbing properties of cellulose sponge can produce defect.The moisture absorbing in cellulose sponge can comprise unwanted microorganism.Once absorb in cellulose sponge, retain, grow and breed in the wet environment that microorganism will be found in cellulose sponge.Microorganism may cause health and safety problem.For example, during clean, the various microbes in cellulose sponge are transferred to other surfaces that user thinks that it is cleaning, and now in fact user is just dispersed in microorganism on other surfaces.
Moreover due to the large water absorption of cellulose sponge, water or other clean solutions a large amount of between flush period can contact cellulose sponge.With many cellulose sponges that antimicrobial is processed, present antimicrobial efficacy, but because rinse or work as goods for clean applications once water, antimicrobial will be washed off from cellulose sponge, so these cellulose sponges do not have long-acting antimicrobial acivity.
Before abandoning, cellulose sponge is by Reusability.Consumer can use cellulose sponge at least one times every day, continue 30 days or more than.In some cases, cellulose sponge can be used twice or more times every day, continue 60 days or more than.In cleaning course, cellulose sponge is often exposed to a large amount of water.Therefore, importantly, the antimicrobial efficacy in cellulose sponge (particularly after a series of flushings) after single is used still keeps.
The microorganism (for example (but being not limited to) that adds biguanides not only to produce in cellulose sponge during packaging partially or completely to kill in cellulose sponge, bacterium, fungi, mould, mould and/or viral) effect, and be created in cellulose sponge and in water, carry out (being preferably at least 50 times for a series of at least 10 times, more preferably at least 100 times) rinse after, still partially or completely kill the effect of the microorganism in cellulose sponge." flushing " is regarded as cellulose sponge to be placed under mobile running water, and water almost soaks into cellulose sponge, excessive water extruded from cellulose sponge, and repeated two to three times.
Put it briefly, applicant finds, although after first use, some biguanides are rinsed out from cellulose sponge at the beginning, but the biguanides of effective dose is still retained in cellulose sponge, to reduce the microorganism in cellulose sponge during the expected service life of cellulose sponge.
Can be comprised in the compound that one or more biguanide compounds in cellulose sponge include, but is not limited to have following general formula:
Figure BPA00001197683100051
X wherein 1and X 2be hydrogen or any aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture.Y 1and Y 2be any aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture.M is equal to or greater than 1 number.Conventionally, M has mean value, and the molecular weight that makes biguanide compound is about 1000-1400 gram/mol; But molecular weight can be higher or lower.Generally speaking, M is about 2-20.Z 1and Z 2hydrogen or the hydrogen that is attached to salt.Above-mentioned organic material can be modified to comprise thiol group in its structure, to allow described compound to be attached on metal matrix, or can directly be fixed on nonmetal substrate allowing with other functional groups are derivative.Above-mentioned organic material is functionalization aptly, to comprise the group such as hydroxyl, amine, halogen, epoxy, alkyl or alkoxysilyl functional group, can directly be fixed to surface.Described salt can comprise: with the salt of inorganic acid, and for example hydrochloride, hydrofluoride, nitrate, sulfate and/or phosphate; And/or for example, such as the organic acid salt of carboxylic acid, acetate, benzoate, tartrate, adipate, lactate, formates, maleate, glutamate, ascorbate, citrate, gluconate, oxalates, succinate, embonate, salicylate, isethionate, succinyl imonium salt, single diethylene glycol (DEG) hydrochlorate, dimethanesulfonate, two isobutyrates and/or gluceptate.The instantiation of these compounds includes, but is not limited to hexamethylene, p-chlorophyenyl biguanide and 4-chlorobenzhydryl biguanide.At this embodiment on the other hand, biguanide compound includes, but is not limited to halo, and oneself is fixed, for example (but being not limited to) Chlorhexidine (1,1 '-hexa-methylene-bis--5-(4-chlorphenyl biguanides) and salt thereof.Biguanides is hexamethylene or a PHMB, and it is by Arch Chemical of Norwalk, and CT is with commodity VANTOCIL IB by name
Figure BPA00001197683100061
aqueous solution form sell.
During the processing of preparing cellulose sponge, some fibre element is oxidized, to produce carboxylate groups.Biguanides is cationic polymer.The electrostatic interaction of the electronegative carboxylate groups of the positively charged site of biguanides in cellulose sponge causes that biguanides is combined.Biguanides is combination securely in cellulose sponge.Yet due to the changeability of input material and processing, the combination degree of biguanides in cellulose sponge may change.Generally speaking, applicant finds, and the biguanides of 40 to 60% in the cellulose sponge of packing (not rinsing) is combined in cellulose sponge.Due to this reason, applicant finds, and biguanides has the long-term efficacy of partially or completely killing the microorganism in cellulose sponge during the expected service life of cellulose sponge.
" used " cellulose sponge has been exposed to a series of flushings.It is to be exposed to the cellulose sponge rinsing for 100 times that used cellulose sponge is confirmed as.Used cellulose sponge must keep the biguanides of floor level, partially or completely to kill the microorganism in cellulose sponge.In addition, biguanide compound content is subject to the restriction that financial cost is considered, formula solubility requires and/or contain the desired use of biguanides product conventionally.
In one embodiment, the input solution that comprises 0.05 to 1.2 % by weight biguanides is absorbed in cellulose sponge, to soak into cellulose sponge.From cellulose sponge, extrude excessive liquid.Generally speaking, after absorbing containing biguanides input solution packing, can not rinse.Before rinsing, comprise by the packing cellulose sponge of the dry weight basis of cellulose sponge at least 0.4 % by weight biguanides and will cause comprising the used cellulose sponge by the dry weight basis of cellulose sponge at least 0.02 % by weight biguanides.For this embodiment, used cellulose sponge remains on the ability that (conventionally in 1 hour, more generally in 5 minutes) in inoculation 24 hours makes 3 logarithm levels of the minimizing of microorganism cellulose sponge in.
In one embodiment, the input solution that comprises 0.1 to 2.0 % by weight biguanides is absorbed in cellulose sponge, to soak into cellulose sponge.From cellulose sponge, extrude excessive liquid.Generally speaking, after absorbing containing biguanides input solution packing, can not rinse.Before rinsing, comprise by the packing cellulose sponge of the dry weight basis of cellulose sponge at least 1.25 % by weight biguanides and will cause comprising the used cellulose sponge by the dry weight basis of cellulose sponge at least 0.5 % by weight biguanides.For this embodiment, used cellulose sponge remains on (conventionally in 1 hour, more generally in 5 minutes) in 24 hours makes microorganism in cellulose sponge reduce by 100% ability.
Alternatively, other antimicrobial and/or antifungal agents can add in cellulose sponge.Optional antimicrobial comprises cationic amine Antimicrobe compound, and it comprises antimicrobial protonated tertiary amine and little molecule quaternary ammonium compound.Quaternary ammonium compound is generally regarded as that gram-positive bacteria (as, staphylococcus) and Gram-negative bacteria (as, Escherichia coli) microorganism is all had to " wide spectrum " antimicrobial cationic compound of effect.Therefore, quaternary ammonium compound can be for cellulose sponge antibiotic object in packing time and adding, and its amount should be effective to this object.The selection of quaternary ammonium compound is not critical.Conventionally it is preferably selected from single long-chain, three short chains, tetraalkyl ammonium compound, two long-chain, two short chain tetraalkyl ammonium compound and their mixture.Described chain can be straight or branched.N-heterocyclic compound is also regarded as season ammoniate.Exemplary little molecule quaternary ammonium compound comprises alkyl benzyl dimethyl ammonium chloride and alkyl-substituted derivative, double long-chain alkyl (C8-C18) quaternary ammonium compound, halogenation hexadecane pyridine and its derivatives, iso-octyl phenoxy group ethoxyethyl group benzyl dimethyl ammonium chloride and alkyl-substituted derivative, Octenidine and their compatible combinations.
When cellulose sponge is wetting, it is relatively soft and pliable and tough.Yet after cellulose sponge is dry, it is hard and stiff.Therefore, cellulose sponge is packaged in sealed plastic wrappage conventionally a little moisteningly.Due to the moisture in packing, before first use, when cellulose sponge is interior in packing, can there is growth of microorganism.Exist the whole bag of tricks to preserve product and improve package stability, comprising and use antimicrobial, anticorrisive agent and disinfection technology.Water activity (a w) be the measuring of energy state of water in system.Water activity is defined as " dissociating " in system sometimes, " constraint " or " available water ".The water activity of controlling packing inner cellulose sponge will be controlled the amount of the water that can promote to pack interior growth of microorganism.Many microorganisms (for example, bacterium) are had a preference for 0.99 water activity level, and great majority need to be grown higher than 0.91.Add wetting agent class salt and sugar " constraint " water to reduce water activity, and therefore control growth of microorganism.Therefore,, in order to preserve cleaning article in packing, can comprise wetting agent to obtain being less than 0.91 water activity.
Except possible antimicrobial impact, comprise wetting agent and can make the cellulose sponge in packing soft and pliable and tough and just can use immediately after unpacking.But once cellulose sponge process is rinsed, wetting agent just can not be retained in cellulose sponge.
In example below, applicant finds, rinse the biguanides of the sponge interior 40 to 60% of packing afterwards and be retained in cellulose sponge, and this reservation seems not depend on the concentration of wetting agent.For the long-time Reusability of cellulose sponge expect to(for) user, it is desirable that antimicrobial is retained in cellulose sponge.Applicant's knowledge shows, the concentration of wetting agent can not affect biguanides and be retained in cellulose sponge, and the amount of wetting agent should for example, be selected based on other factors (, wetting agent is given required water activity or required " pliability " of packing cellulose sponge).
Exist several different methods that wetting agent is introduced in cellulose sponge.A kind of method can be wetting agent to be included in the input solution absorbing in cellulose sponge before packing.Biguanides can be included in wetting agent solution, or biguanides can be absorbed in the plain sponge of dimension before or after wetting agent is introduced in cellulose sponge.
Suitable wetting agent can comprise cationic salts.Salt is desirable wetting agent, because compared with permitting eurypalynous cationic antimicrobial agent, this compounds general cost is low.Can use multiple different salt, such as (but being not limited to) monovalent salt, divalent salts, organic salt etc.These salt include, but is not limited to acetate, acetylide, ammonium salt (not comprising quaternary ammonium salt), arsenate, astatine salt, azide, dihalide salt, bicarbonate, disulphide, boride, boron hydride, boron halide, carbonate, citrate, cyanate, cyanide, formates, germanate, glycinate, halate, halide, hydride, hydrogen selenides, sulfhydrate, hydroxide, acid imide, metaniobate, inclined to one side tantalates, metavanadate, nitrate, nitride, nitrite, oxide, perchlorate, phosphate, phosphonium salt, selenides, selenite, selenate, sulfide, sulfate, ternary salt, tetraalkylammonium salt, tellurides, rhodanate, and/or vanadate.Aspect the Yi Ge of this embodiment, antimicrobial includes, but is not limited to salicylate, magnesium sulfate, magnesium chloride, sodium chloride, ammonium chloride and/or the potassium chloride of potassium citrate, natrium citricum, sodium tartrate, potassium tartrate, potassium lactate, sodium lactate, sodium and/or potassium.
In one embodiment, wetting agent is MgCl 2.If comprise MgCl 2realize the water activity that is less than 0.91, at least 10 % by weight of inputting solution should be MgCl 2.Yet too high wetting agent can cause precipitation.Therefore, MgCl 2if (comprising) should be no more than 14 % by weight of input solution.
In order to prepare antimicrobial fibre element sponge as described in the present disclosure, the regenerated cellulosic sponge of flushing is exposed to the input solution that comprises biguanides.The regenerated cellulosic sponge of rinsing generally has the water content of 40 to 70% water.Or, containing biguanides input solution, can be absorbed in dry cellulose sponge.Input solution is absorbed by cellulose sponge, and soaks into cellulose sponge.Generally speaking, the biguanides that input solution comprises 0.05 to 2.0 % by weight, so that used cellulose sponge keeps the biguanides of enough content, partially or completely to kill the microorganism in cellulose sponge.Input solution can additional packets contain wetting agent or other antimicrobials.Or wetting agent or other antimicrobials (if comprising) can be introduced into and absorb in cellulose sponge before absorbing biguanides or after absorbing biguanides.
After in input solution is absorbed into cellulose sponge, from cellulose sponge, extrude excessive liquid.Then, cellulose sponge can be converted into appropriate size, and is packaged in diaphragm seal.In one embodiment, the cellulose sponge of packing comprises conventionally by the biguanides of the dry weight basis of cellulose sponge at least 0.4 % by weight, so that the biguanides of dry weight basis at least 0.02 % by weight of cellulose sponge is pressed in used cellulose sponge maintenance, this amount is enough to partially or completely kill the microorganism in cellulose sponge.In another embodiment, the cellulose sponge of packing comprises conventionally by the biguanides of the dry weight basis of cellulose sponge at least 1.25 % by weight, so that the biguanides of dry weight basis at least 0.5 % by weight of cellulose sponge is pressed in used cellulose sponge maintenance, this amount is enough to partially or completely kill the microorganism in cellulose sponge.
Although show herein and described specific embodiments more of the present invention, should be appreciated that these embodiment are only programmable many possible concrete structures while exemplarily having shown the application principle of the invention.Those skilled in the art can design many other different structures without departing from the spirit and scope of the present invention according to these principles.Therefore, scope of the present invention should not be limited to the structure described in present patent application, and only should be subject to the restriction of structure described in the word in claim and its equivalent structure.
example
the preparation of antimicrobial solutions
The biguanides solution of commercially available 20 % by weight of dilute with water (Vantocil IB, hexamethylene derive from Arch Chemical Company of Cheshire, Connecticut), to obtain required biguanides concentration.
the preparation of cellulose sponge
By common process (utilizing the adhering process of electrocoagulation), prepare cellulose sponge piece.Then, change and packing before, cellulose sponge piece is with hot water injection, with the aqueous solution bleaching containing hypochlorite, water rinses, and with magnesium chloride (MgCl 2) rinse.Or, use the cellulose sponge of packing, for example, derive from 3M Company of St.Paul, the O-Cel-O of MN
Figure BPA00001197683100111
sponge or Scotch-Brite
Figure BPA00001197683100112
shampooing sponge.
For any in above-mentioned cellulose sponge, by cellulose sponge being placed under mobile running water, water almost soaks into cellulose sponge, with hand, excessive moisture is extruded from cellulose sponge, and is repeated 50 times, to obtain the cellulose sponge of preparation.
biguanides adds cellulose sponge
Contain or do not contain MgCl 2the biguanide compound of solution form be absorbed in the cellulose sponge of preparation, to soak into cellulose sponge and to form antimicrobial fibre element sponge.From cellulose sponge, extrude excessive liquid.From cellulose sponge, extract biguanides, and by the biguanides of absorptiometry (by Beckman Instruments Inc.of Fullerton, Beckman DU 640 spectrophotometers that CA buys) Test extraction solution.
method of testing and material
According to following methods, be evaluated at the goods of preparing in following instance.
water rinses rules
The simulation water flushing rules of used sponge comprises: by water saturates, contain biguanides cellulose sponge and with hand, wring out the cellulose sponge soaking into subsequently.Generally speaking, water is mobile running water.Repeat rinse and wring out circulation, the number of times being cycled to repeat is pointed out in data.Generally speaking, rinsing and wring out circulation is repeated 50 or 100 times.
killing bacteria is analyzed (with reference to AATCC 100)
" kill analysis " or the effect at predetermined time period antimicrobial is determined in anticorrisive agent test.The minimizing of 3 logarithm levels of the micro organism quantity of object to be measured is normally introduced in the indication of the passing through of this test/unsuccessfully.
The cellulose sponge of preparation absorbs containing biguanides input solution, then carries out water and rinses rules, to allow to assess the durability of the antimicrobial treatment of cellulose sponge.In this test, water rinses rules and relates to cellulose sponge is immersed in deionized water, rather than under mobile running water.Then, sample is placed in polybag.
At turbidity, be equal in the 0.1% peptone water solution that turbidity standard is identical and prepare the bacterial suspension using in described test with 0.5McFarland.This standard produces every milliliter about 1.5 * 10 conventionally 8the total number of bacteria of CFU (CFU).Cellulose sponge sample is cut into 1.5 " * 2.5 " * 1.0 " inch size (surface area 3.75in 2).Cellulose sponge copies and supplies.The test organism of using is as follows:
A. (ATCC 14028 for Salmonella choleraesuls hog cholera subspecies mouse typhus serotype; In ATCC storehouse, be called Salmonella enteritidis enteron aisle subspecies now)
B. pseudomonas aeruginosa (ATCC 15442) or pseudomonas putida
C. staphylococcus aureus (ATCC 6538)
D. Escherichia coli (ATCC11229)
E. Shewanella putrefaciens (ATCC 8071)
Test cellulose sponge is placed in the Whirlpak of sterilization tMin bag.100 μ L kind bacterium are added in the peptone water of 22mL, and for inoculating cellulose sponge.For mixed cell, the cellulose sponge in bag is manually pushed repeatedly, so that bacterial suspension distributes equably and allow liquid heavily to absorb in cellulose sponge.Allow the bag that cellulose sponge is housed under room temperature (20-25 ℃), to cultivate in whole experiment.For 24 hours readings of zero-sum, after the time of contact of 5 minutes and 24 hours, measure cellulose sponge bacterial community respectively.
In the postvaccinal following time, cellulose sponge is sampled: 5 minutes (after inoculation, carrying out immediately) and 24 hours.From cellulose sponge, extrude liquid, and from bag, extract 100 μ L solution out.Extract is placed in the peptone water of 9.9mL, and mixes by eddy current.Serial dilution thing is coated over 3M Petrifilm tMtest pieces (1mL) is upper, until reach isarithmic scope.Test pieces is cultivated 24 hours at 35 ℃, and utilizes 3M Petrifilm tMtest pieces reader (plate reader) is counted.
fungi attack test (with reference to ASTM G21-96)
The cellulose sponge of preparation absorbs containing biguanides input solution, then carries out water and rinses rules, to allow to assess the durability of the antimicrobial treatment of cellulose sponge.In this test, water rinses rules and relates to cellulose sponge is immersed in deionized water, rather than under mobile running water.Then, sample is placed in polybag.
With standardized method of testing ASTM G21-96, by by the mixed fungus spore suspension aerosolization of concentration known on sample surfaces, and material is cultivated 28 days under 28 ℃/95% relative humidity, test cellulose sponge.Test cellulose sponge is placed on the surface of micro-salt (M-9) agar test pieces under aseptic condition, and inoculation.The medium using does not comprise carbon source.Therefore, the growth of fungi shows the destruction of sample component.Following organism is used in standard testing:
Fungi ATCC No.
Aspergillus aspergillus 9642
Have a liking for loose mould 11797
Chaetomium globosum 6205
Green sticky broom bacterium 9645
Aureobasidium pullulans 15233
In the postvaccinal following time, cellulose sponge is sampled: the 5th day, the 12nd day, the 15th day and the 29th day.Whether the cellulose sponge of checkout there is conk, and evaluation level of growth as follows.Also a sterilized filter paper is inoculated, to be used as front tester.
Measuring scale: 0 not growth
1 0-10% coverage, trace growth
2 10-30% coverages, slightly growth
3 30-60% coverages, gentle growth
4 > 60% coverages, raised growth
water activity (a in cellulose sponge w )
Water activity (a w) be the measurement of the amount of the microorganism free water that can be used for supporting growth.Water activity represents the active part of the water content relative with the total moisture content that comprises " irreducible water ".By use, be used for determining the mirror surface condensing dew point hygrometric method of water activity, utilize Decagon Devices, the AquaLab CX-2 of Inc. measures.Cellulose sponge is cut into the " dish of inch diameter and 1/16 inch thickness that has 1.5.
example
Following instance further illustrates aspect of the present invention.Except as otherwise noted, all umbers and percentage are all by weight.
example 1
By the liquid biguanides solution of table 1 being absorbed in the cellulose sponge of preparation to soak into cellulose sponge, described liquid biguanides solution is introduced to cellulose sponge, and cellulose sponge is laminated to scouring web.From cellulose sponge, extrude excessive solution, and cellulose sponge is placed in to packing.Then, cellulose sponge is carried out to water and rinse rules, and indicate the number of times that rinses/wring out circulation, to simulate used cellulose sponge.
table 1: biguanides solution
Figure BPA00001197683100141
According to described killing bacteria analysis and fungi attack test, test cellulose sponge.Data are presented on table 2 to table 4.
table 2: killing bacteria analysis (AATCC 100)
Figure BPA00001197683100151
*may be active due to antimicrobial, test pieces on the first dilution without any growth.
*used=rinse/wring out circulation 100 times
table 3: the fungi of cellulose sponge is attacked (ASTM G21-96)
Figure BPA00001197683100152
table 4: the fungi with the cellulose sponge of scouring web is attacked (ASTM G21-96)
Figure BPA00001197683100161
example 2
By soaking 20 minutes in the solution of one of given formula of the cellulose sponge of preparation table 5 below comprising, prepare antimicrobial fibre element sponge.Can also be by the cellulose sponge of preparation is soaked 20 minutes in input biguanides solution, then at MgCl 2in solution, soak and be less than 5 minutes, prepare antimicrobial fibre element sponge.After immersion, cellulose sponge is extruded between compression roller, is then placed in immediately in polybag for packing.
Flushing rules comprise: cellulose sponge is soaked in a large amount of deionized waters, then wring out the cellulose sponge soaking into, the flushing of each sample/wring out circulation to be repeated nearly 10 times.Then, sample is placed in polybag.
table 5: with the biguanides solution of wetting agent
Component formula
Biguanides 0.05%-2%
MgCl2 1%-14%
NaCl 1%-16%
Water is added into 100%
The data that table 6 presents show, the concentration of wetting agent seems can not produce a very large impact rinsing the reservation of biguanides in rear cellulose sponge.Comparison between biguanides after retaining the biguanides in the cellulose sponge (not rinsing) that relates to packing and rinsing and wring out circulation for 10 times in cellulose sponge.
table 6: the biguanides in cellulose sponge retains
Figure BPA00001197683100171
example 3
Commercially available magnesium chloride hexahydrate (MgCl 2.6H 2) (EMD Chemical Company, Gibbstown, New Jersey), sodium chloride (NaCl) (Fisher Scientific Company, Fair Lawn, New Jersey), potassium chloride (KCl) (EMD Chemical Company, Gibbstown, New Jersey) and glycerine (EMD Chemical Company, Gibbstown, New Jersey) mixed, to obtain required concentration.Utilize Decagon Devices, the AquaLab CX-2 of Inc. measures the water activity of solution.The water activity of these solution is presented in table 7.
table 7: the water activity of various wetting agent solution
Figure BPA00001197683100181
example 4
The cellulose sponge of preparation is at the MgCl of example 3 2or soak 20 minutes in one of NaCl wetting agent solution.After immersion, cellulose sponge is extruded between compression roller, is then placed in immediately in airtight polybag.Water activity at 24 hours build-in test samples.
Magnesium chloride and sodium chloride have reduced the water activity level of cellulose sponge.The data that present in table 8 show, the MgCl of the enough concentration in can water 2with NaC, the water activity of cellulose sponge is reduced to below 0.91.
table 8: the water activity of various wetting agents in cellulose sponge
Figure BPA00001197683100191

Claims (13)

1. a method for the structure that keeps clean anti-microbe ability, described method is comprised of following steps:
The cellulose sponge of anionic functional is provided;
Wherein anionic functional group forms during manufacturing cellulose sponge;
To be absorbed in described cellulose sponge by water and the input solution that the biguanides with Cationic functional groups forms;
The described Cationic functional groups of described biguanides and the described anionic functional group of described cellulose sponge are combined;
During the described cellulose sponge having in conjunction with the biguanides on it is packaged in and is packed;
Wherein the cellulose sponge of packing optionally comprises the material that is selected from dyestuff, spices, aromatic, surfactant and fortifying fibre;
Wherein the cellulose sponge of packing does not comprise NMF; And
Wherein water carries out rinsing and wringing out for 100 times after circulation, and cellulose sponge keeps by the biguanides of the combination of dry weight basis at least 0.02 % by weight of described cellulose sponge, to obtain the minimizing of at least 3 logarithm levels of microorganism in described cellulose sponge.
2. method according to claim 1, in wherein said cellulose sponge, the described minimizing of microorganism occurred in 5 minutes.
3. method according to claim 1, wherein water carries out 100 times and rinses and wring out after circulation, cellulose sponge keeps by the biguanides of the combination of dry weight basis at least 0.5 % by weight of described cellulose sponge, to obtain 100% minimizing of microorganism in described cellulose sponge.
4. method according to claim 1, wherein by the dry weight basis of described cellulose sponge, the biguanides of the combination that the cellulose sponge of packing comprises at least 0.4 % by weight.
5. method according to claim 4, wherein by the dry weight basis of described cellulose sponge, the biguanides of the combination that the cellulose sponge of packing comprises at least 1.25 % by weight.
6. method according to claim 4, wherein water carries out 100 times and rinses and wring out after circulation, cellulose sponge keeps by the biguanides of the combination of dry weight basis at least 0.5 % by weight of described cellulose sponge, to obtain 100% of microorganism minimizing in described cellulose sponge in 5 minutes.
7. method according to claim 1, the compound that wherein biguanides is following general formula:
Figure FDA0000377176720000021
Wherein:
X 1and X 2be hydrogen or aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
Y 1and Y 2be aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
M is equal to or greater than 1 number; And
Z 1and Z 2hydrogen.
8. a method of preparing antimicrobial cleansing goods, described method is comprised of following steps:
The cellulose sponge of anionic functional is provided;
Wherein anionic functional group forms during manufacturing cellulose sponge;
The main input solution consisting of the biguanides with Cationic functional groups of water and at least 0.1 % by weight is absorbed in described cellulose sponge;
The described Cationic functional groups of described biguanides and the described anionic functional group of described cellulose sponge are combined;
During the described cellulose sponge having in conjunction with the biguanides on it is packaged in and is packed, wherein by the dry weight basis of described cellulose sponge, the biguanides that the cellulose sponge of packing comprises at least 0.4 % by weight;
Wherein the cellulose sponge of packing optionally comprises the material that is selected from dyestuff, spices, aromatic, surfactant and fortifying fibre;
Wherein the cellulose sponge of packing does not comprise NMF.
9. method according to claim 8, the compound that wherein biguanides is following general formula:
Figure FDA0000377176720000031
Wherein:
X 1and X 2be hydrogen or aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
Y 1and Y 2be aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
M is equal to or greater than 1 number; And
Z 1and Z 2hydrogen.
10. the antimicrobial cleansing goods of the packing of being prepared by the method for claim 8.
The antimicrobial cleansing goods of 11. packings of being prepared by the method for claim 9.
12. 1 kinds of antimicrobial sponges, it is substantially by cellulose sponge, water and the biguanides of being combined with described cellulose sponge form, described biguanides is combined with described cellulose sponge anionic functional group's on described cellulose sponge by the Cationic functional groups in biguanides interaction, wherein after water carries out rinsing for 100 times and wrings out circulation, described cellulose sponge keeps by the biguanides of the combination of dry weight basis at least 0.02 % by weight of described cellulose sponge, to obtain the minimizing of at least 3 logarithm levels of microorganism in described cellulose sponge; Wherein cellulose sponge optionally comprises the material that is selected from dyestuff, spices, aromatic, surfactant and fortifying fibre; And cellulose sponge wherein does not comprise NMF.
13. antimicrobial sponges according to claim 12, the compound that wherein biguanides is following general formula:
Figure FDA0000377176720000041
Wherein:
X 1and X 2be hydrogen or aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
Y 1and Y 2be aliphatic, cyclic aliphatic, aromatic series, replacement aliphatic, substituted aromatic, heterolipid family, heterocycle or heteroaromatics or any these mixture;
M is equal to or greater than 1 number; And
Z 1and Z 2hydrogen.
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